CN101571523A - Method for measuring various types of unknown pollutants in sewage - Google Patents
Method for measuring various types of unknown pollutants in sewage Download PDFInfo
- Publication number
- CN101571523A CN101571523A CNA2009100984669A CN200910098466A CN101571523A CN 101571523 A CN101571523 A CN 101571523A CN A2009100984669 A CNA2009100984669 A CN A2009100984669A CN 200910098466 A CN200910098466 A CN 200910098466A CN 101571523 A CN101571523 A CN 101571523A
- Authority
- CN
- China
- Prior art keywords
- sewage
- temperature
- pollutants
- split ratio
- keeps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for applying a gas phase chromatography-combined with gas spectrometry to measure various types of unknown pollutants in sewage, belonging to the technical field of environmental detection. The invention firstly proposes a method for synchronous extraction and pretreatment; the sewage applies the gas phase chromatography-combined with gas spectrometry after being treated by purification and concentration and the specific parameters of measuring work with gas phase chromatography-combined with gas spectrometry are respectively proposed. By the analysis of the above instruments, an obtained molecular fragment peak value is compared with an NIST library, and then the qualitative analysis can be made to a plurality of unknown pollutants so as to determine the pollutants and have important functions for finding the sources of the pollutants and investigation, handling and identification of pollution accidents.
Description
Technical field
The invention discloses a kind of method of measuring multiple types of unknown pollutants in the sewage, belong to the environment measuring technical field.
Background technology
Along with China's economy develop rapidly, each industry heats up rapidly, industrial development is especially outstanding, this just inevitably brings some negative effects, comprise pollution to environment, only all will cause loss more than several hundred million yuan every year to the pollution of fishery ecologic environment, the accident polluting that discharge of industrial wastes causes takes place again and again.But the authenticate technology of accident development is slow relatively, particularly pollution source determine and dirt qualitative aspect, often, accident is identified is lagged behind because data support does not timely cause lack of evidence, accident can not get dealing carefully with, and causes the certain social problem.
Traditional detection method such as gas chromatography, liquid chromatography, spectrophotometric method etc. are often felt simply helpless in the face of unknown pollutant, perhaps can only carry out analyzing and testing to a pollutant.And from contaminated actual, multiple often rather than single pollutant is playing contamination, thereby above-mentioned method is the current reality of incompatibility.
During types of unknown pollutants, sample pre-treatments mainly is to separate determinand and matrix in order to reach, and determinand is carried out purifying, enrichment, reduces the influence of other materials to instrument detecting in analyzing sewage.Aspect sewage analaysis, mostly adopt liquid-liquid extraction to combine with Solid-Phase Extraction, but this method can not extract the different types of unknown pollutants of character simultaneously, as extracting and need repeatedly handle multiple types of unknown pollutants, has so not only influenced ageing but also has increased the laboratory cost.Thereby, the improved needs of raising are arranged.And nearly GC-MS(gas chromatography-mass spectrography) that began to use in 2 years can solve the problem of this respect well.The GC-MS method can detect polytype pollutant simultaneously, and can be accurately qualitative, quantitative to detected object.
Summary of the invention
For solving the technology that present traditional detection technique can not detect, analyze multiple types of unknown pollutants, though and the GC-MS method can detect polytype pollutant simultaneously, extracting pretreatment technology simultaneously is the problem that must at first solve.The present invention will find a kind of method that can carry out pre-treatment simultaneously to types of unknown pollutants, this method both can not cause background interference to follow-up instrument detecting, the analytical approach that is set by instrument in the time of carrying out qualitative analysis to types of unknown pollutants is again accepted, what be that the first step of the present invention will solve is the pre-treating method that extracts simultaneously, on this basis, second step was a mensuration running parameter of selecting gas chromatography-mass spectrography, thereby finished purpose of the present invention.
The pretreatment technology that extracts simultaneously of the present invention is as follows: behind 500mL sewage mechanical filter, water sample places separating funnel, divide three extractions with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3, a with 0.125mol/L sodium hydroxide solution accent pH to 11, extract purifies with the 30g/L metabisulfite solution.Again two parts of extracts are passed through alumina chromatographic column, collect filtered fluid and be concentrated into 2mL at 40 ℃ of water-bath rotary evaporations, standby.
Above-mentioned concentrate is after treatment carried out the qualitative analysis of types of unknown pollutants.The instrument that uses is a gas chromatography-mass spectrography, the vaporizer temperature of traditional analysis method is constant high temperature, gas phase of the present invention partly utilizes the temperature programme of vaporizer that the pollutant of different boiling can not decomposed under different temperature conditions, and the temperature programme of gas chromatographic column can be separated each pollutant preferably.The mensuration running parameter of gas chromatography: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃, keep 1min, initial split ratio 1: 20,0.01min split ratio 1: 100,0.75min the split ratio of closing, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min.Running parameter is measured in the mass spectrum aspect: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.By comparing, just can correctly carry out qualitative at last to types of unknown pollutants in the sewage with the NIST storehouse.On positive determinacy basis, can seek the source of pollutant, to the evaluation of contamination accident, handle important evidential function is arranged to pollutant.Its advantage is: simple to operate, practical, good separating effect, pretreatment technology is enhanced about more than once analyzing and testing efficient simultaneously, can be used as the foundation that contamination accident is handled.
Specific implementation method
At first, extract pre-treating method simultaneously: get the sewage 500ml that needs detection, with 500ml sewage through mechanical filter, filtered sewage is placed separating funnel, divide three extractions with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3, a with 0.125mol/L sodium hydroxide solution accent pH to 11, extract purifies with the 30g/L metabisulfite solution.Again two parts of extracts are passed through alumina chromatographic column, collect filtered fluid and be concentrated into 2mL at 40 ℃ of water-bath rotary evaporations, standby.
Second step: use gas chromatography-mass spectrography above-mentioned treated sewage is carried out qualitative analysis, its mensuration running parameter is:
1, gas chromatography parameter: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃, keeps 1min, initial split ratio 1: 20, and 0.01min split ratio 1: 100,0.75min closes split ratio, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min.
2, mass spectrum parameter: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.
With scanning result, by comparing, just can correctly carry out qualitatively to multiple types of unknown pollutants in the sewage with the NIST storehouse, just can determine which hazards of pollutants.
By the invention described above method many contamination accidents are detected, detected classes of compounds such as group thiophosphate, pyrazoles, organophosphorus pesticide class, chrysanthemum ester class, pyridines, benzene series thing and chlorobenzene class, phenol, phenyl amines, for the contaminated solution accident provides the data support.Blank interpolation test is carried out to 48 kinds of organophosphoruss and organo-chlorine pesticide in the laboratory, and utilization the inventive method is carried out check and analysis, and 48 kinds of organism all detect, detection limit scope 0.02 μ g/L-0.2 μ g/L.
Aspect the caused legal dispute of contaminated solution,, support the present invention of following illustration is arranged simultaneously by the enforcement of the invention described above:
Illustration 1:2004, mass mortality repeatedly appears in the aquaculture organism in Longwan District mudflat aquaculture district, Wenzhou City, Zhejiang Province, loss surpasses 1,000 ten thousand yuan, suspects relevantly with near the blowdown of industrial park, but this industrial park does not provide the condition of production and the pollutant data of factory.By the waste water of gathering this Craft in Chemical Industrial Area sewage draining exit, the seawater of culture zone, measure and analyze according to method of the present invention, in waste water and culture zone seawater, all detect agricultural chemicals and a large amount of agricultural chemicals synthetic intermediate, raw materials such as chlopyrifos, methidathion, Hostathion.Confirm through searching data, there is overt toxicity in these chemical substances to the biology of culture zone, confirm through social investigation simultaneously, be this industrial park relevant enterprise with the detected organism of this method and produce product, raw material, intermediate, thereby the death of very fast affirmation breed garden aquatic biological causes just because of the industrial park blowdown.
Illustration 2:2005, the white shrimp mass mortality of spine end of culturing in the pool in the white shrimp aquaculture of Putuo District, Zhoushan City, Zhejiang Province spine end field lose hundreds thousand of units, and near the shrimp that other culture the pool is all safe and sound, and the raiser is very puzzled to the cause of death of the white shrimp of spine end.The inventor has gathered in this breed pool 1 bottle of water sample, carries out check and analysis according to the inventive method, detects to contain Hostathion and two kinds of agricultural chemicals to the high poison of the white shrimp of spine end of sulfotep in the water body, and clue is investigated in view of the above, is that agricultural chemicals is improper to be caused because near peasant household uses.
Illustration 3:2007, the Penaeus Vannmei generation mass mortality that the Putuo District, Zhoushan City, Zhejiang Province raiser cultures is lost more than 10 ten thousand yuan, and the raiser suspects has the people to poison, and reports public security organ immediately, but because of pollutant is not clear investigation is had reached an impasse.The inventor has gathered water sample in this breed pool, carries out check and analysis according to the inventive method, detects fenvalerate in water body.Clue in view of the above, public security organ has arrested the molecule of poisoning very soon, makes it obtain the sanction of law.
Claims (1)
1, a kind of method of measuring multiple types of unknown pollutants in the sewage is characterized in that, this method follows these steps to operation:
One, extract pre-treating method simultaneously, get the sewage 500ml that needs detection, with 500ml sewage behind mechanical filter, filtered sewage is placed separating funnel, with methylene chloride-sherwood oil mixed liquor 40mL, 40mL, 20mL divides three extractions, behind the combining extraction liquid extract is divided into two parts, a with 0.1mol/L sulfuric acid accent pH to 3, a with 0.125mol/L sodium hydroxide solution accent pH to 11, extract purifies with the 30g/L metabisulfite solution, again two parts of extracts are passed through alumina chromatographic column, collect filtered fluid and be concentrated into 2mL at 40 ℃ of water-bath rotary evaporations;
Two, use gas chromatography-mass spectrography, the concrete mensuration running parameter of instrument is:
A, gas chromatography parameter: the injection port initial temperature is a normal temperature, keeps 0.75min, and 200 ℃/min rises to 280 ℃, keeps 1min, initial split ratio 1: 20, and 0.01min split ratio 1: 100,0.75min closes split ratio, 3.00min split ratio 1: 100; Column flow rate 1.2mL/min; Temperature programme, 55 ℃ of initial column temperatures are kept 1min, and 5 ℃/min is warming up to 280 ℃, keeps 14min;
B, mass spectrum parameter: 200 ℃ of ion trap temperature; 45 ℃ of menifold temperature; 200 ℃ of transmission line temperature; Ionization mode: EI, 70ev; Solvent delay 10min; Sweep limit 40～650, autoscan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100984669A CN101571523B (en) | 2009-05-07 | 2009-05-07 | Method for measuring various types of unknown pollutants in sewage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100984669A CN101571523B (en) | 2009-05-07 | 2009-05-07 | Method for measuring various types of unknown pollutants in sewage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101571523A true CN101571523A (en) | 2009-11-04 |
| CN101571523B CN101571523B (en) | 2012-04-11 |
Family
ID=41230926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100984669A Expired - Fee Related CN101571523B (en) | 2009-05-07 | 2009-05-07 | Method for measuring various types of unknown pollutants in sewage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101571523B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183596A (en) * | 2011-03-02 | 2011-09-14 | 江南大学 | Method for detecting antibiotic residue in honey based on rapid classification extraction technology |
| CN104502497A (en) * | 2014-12-04 | 2015-04-08 | 苏州国环环境检测有限公司 | Method for detecting residual methidathion in ripe orange |
| WO2015109365A1 (en) * | 2014-01-24 | 2015-07-30 | Waterup Pty Ltd | A system for environmental spills protection |
| CN108061681A (en) * | 2017-12-25 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | The detection method of Manganese in Waste Water ion |
| CN111537651A (en) * | 2020-06-16 | 2020-08-14 | 青岛海关技术中心 | Method for detecting heavy oil pollutants in aquatic products |
| CN113945650A (en) * | 2021-09-09 | 2022-01-18 | 国家粮食和物资储备局科学研究院 | Method for simultaneously analyzing persistent organic pollutants in grains |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100538354C (en) * | 2007-01-12 | 2009-09-09 | 清华大学 | A kind of method that detects estrogen active contribution in the sewage |
-
2009
- 2009-05-07 CN CN2009100984669A patent/CN101571523B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183596A (en) * | 2011-03-02 | 2011-09-14 | 江南大学 | Method for detecting antibiotic residue in honey based on rapid classification extraction technology |
| WO2015109365A1 (en) * | 2014-01-24 | 2015-07-30 | Waterup Pty Ltd | A system for environmental spills protection |
| CN104502497A (en) * | 2014-12-04 | 2015-04-08 | 苏州国环环境检测有限公司 | Method for detecting residual methidathion in ripe orange |
| CN104502497B (en) * | 2014-12-04 | 2016-05-25 | 苏州国环环境检测有限公司 | The residual detection method of methidathion in a kind of ripe orange |
| CN108061681A (en) * | 2017-12-25 | 2018-05-22 | 大工（青岛）新能源材料技术研究院有限公司 | The detection method of Manganese in Waste Water ion |
| CN111537651A (en) * | 2020-06-16 | 2020-08-14 | 青岛海关技术中心 | Method for detecting heavy oil pollutants in aquatic products |
| CN113945650A (en) * | 2021-09-09 | 2022-01-18 | 国家粮食和物资储备局科学研究院 | Method for simultaneously analyzing persistent organic pollutants in grains |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101571523B (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101571523B (en) | Method for measuring various types of unknown pollutants in sewage | |
| Kellerman et al. | Unifying concepts linking dissolved organic matter composition to persistence in aquatic ecosystems | |
| Okoffo et al. | Identification and quantification of selected plastics in biosolids by pressurized liquid extraction combined with double-shot pyrolysis gas chromatography–mass spectrometry | |
| Xu et al. | Investigation on extracellular polymeric substances from mucilaginous cyanobacterial blooms in eutrophic freshwater lakes | |
| Al-Saleh et al. | Assessing the concentration of phthalate esters (PAEs) and bisphenol A (BPA) and the genotoxic potential of treated wastewater (final effluent) in Saudi Arabia | |
| Yang et al. | Preservation of lipid hydrogen isotope ratios in Miocene lacustrine sediments and plant fossils at Clarkia, northern Idaho, USA | |
| Shao et al. | Fluorescent natural organic matter fractions responsible for ultrafiltration membrane fouling: Identification by adsorption pretreatment coupled with parallel factor analysis of excitation–emission matrices | |
| Zhou et al. | Variability in dissolved organic matter composition and biolability across gradients of glacial coverage and distance from glacial terminus on the Tibetan Plateau | |
| Ma et al. | Molecular structure and evolution characteristics of dissolved organic matter in groundwater near landfill: implications of the identification of leachate leakage | |
| Li et al. | Distribution and removal of fluorescent dissolved organic matter in 15 municipal wastewater treatment plants in China | |
| ATE294383T1 (en) | DEVICE AND METHOD FOR DETECTING ORGANIC MOLECULES IN A SAMPLE SUBSTANCE | |
| CN108008048A (en) | The pollution source discrimination of emerging pollutant and application in a kind of ground water regime | |
| CN103529145A (en) | Method for fast identifying key quasi/anti-androgen interference poison in water sample | |
| EP1376124A3 (en) | Toxin detection and compound screening using biological membrane microarrays | |
| CN104280483A (en) | Pretreatment method for detecting chloromycetin in animal product | |
| Quevauviller et al. | Method performance evaluation for methylmercury determination in fish and sediment | |
| Dürig et al. | Novel prioritisation strategies for evaluation of temporal trends in archived white-tailed sea eagle muscle tissue in non-target screening | |
| CN109142264A (en) | The method that oil field sludge oil content determines | |
| CN114002340A (en) | Method for detecting petroleum hydrocarbon in polluted soil | |
| CN113552244A (en) | ASE-Py-GCMS-based method for determining qualitative and quantitative properties of nano micro plastic | |
| Facca et al. | Harmful algae records in venice lagoon and in Po river delta (northern adriatic sea, Italy) | |
| CN102798656B (en) | Method for separating 3-hydroxyl glutaric acid monoester enantiomer by high-performance capillary electrophoresis | |
| CN111551658A (en) | Rapid detection and analysis method for antihistamine medicines in water body | |
| CN103901139A (en) | Pretreatment method for analyzing tetrabromobisphenol A in biologic urine | |
| Ivankovic et al. | Multiclass determination of drug residues in water and fish for bioaccumulation potential assessment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120411 Termination date: 20170507 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |